CN112480672B - Colorless transparent polyimide film and preparation method thereof - Google Patents
Colorless transparent polyimide film and preparation method thereof Download PDFInfo
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- CN112480672B CN112480672B CN202011355207.2A CN202011355207A CN112480672B CN 112480672 B CN112480672 B CN 112480672B CN 202011355207 A CN202011355207 A CN 202011355207A CN 112480672 B CN112480672 B CN 112480672B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
Abstract
The invention discloses a colorless transparent polyimide film and a preparation method thereof, belonging to the technical field of polyimide materials. The colorless transparent polyimide film contains 2-10 mol% of structural units shown in formula (I), and the colorless transparent polyimide film has a lower dielectric loss factor; by doping 2-8 wt% of glass powder in the colorless transparent polyimide film, the light transmittance of the film is maintained (above 88%), the pencil hardness of the obtained film is improved to be above 3H, and the CTE of the obtained film is reduced to be below 32 ppm/K; moreover, the film can be prepared by adopting the traditional imidization process of the PI film, so that the process is simplified, and the efficiency is higher. Wherein the structural unit shown in the formula (I) is as follows:
Description
Technical Field
The invention relates to a polyimide material, in particular to a colorless transparent polyimide film and a preparation method thereof.
Background
With the increasing development of optical devices to be light, thin, lightweight, flexible and high-frequency, the inorganic transparent glass material of the traditional display substrate is eliminated due to heavy weight, fragility and incapability of bending, and the transparent flexible polymer transparent engineering plastic material such as polyethylene terephthalate (PET) cannot meet the high-temperature processing requirement of the flexible substrate at the temperature of more than 300 ℃ due to low heat resistance, so that the application of the material in the optical display field is limited. The colorless transparent polyimide (CPI) film has excellent heat resistance, is easy to bend and has good transparency, and becomes a necessary material in the field of optical display. However, in order to improve the service life, the optical display has high requirements on the surface scratch resistance of the colorless transparent polyimide film, which is far higher than that of a plastic film with pencil hardness less than or equal to H; meanwhile, the Coefficient of Thermal Expansion (CTE) of the colorless polyimide film and the CTE (copper is 17 ppm/K) of the metal material are close, and the phenomena of interlayer cracking and warping caused by temperature change are avoided, so that the use reliability of the electronic device is further influenced. Therefore, it has been a hot point of research to increase the pencil hardness of the surface of the colorless and transparent polyimide film and to reduce the CTE.
At present, two main methods for reducing the surface hardness of the colorless transparent polyimide film are available: one method is a surface coating hardening layer method, which comprises thermosetting organic silicon and Ultraviolet (UV) cured acrylate, and a colorless transparent polyimide film has very low surface energy because most of molecular structures contain fluorine atoms, is difficult to be firmly combined with a coating layer, and is difficult to meet the requirement of testing the adhesive force grade by adopting a grid marking method. The invention patent of publication No. CN110467739A discloses that by coating a UV-cured hardened layer on the surface of a CPI film, the pencil hardness reaches 4H-5H, but the adhesion is not mentioned; the other method is a method of compounding with a high-hardness filler, in which a high-hardness filler (e.g., ceramic powder, silicon nitride, or silicon dioxide) is added to a polyamic acid resin to increase the surface pencil hardness, but the light transmittance of the film is reduced and the optical requirements cannot be satisfied. Therefore, increasing CPI surface hardness becomes a technical bottleneck at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a colorless transparent polyimide film which has higher pencil hardness, low dielectric property and low CTE and is simple in process and a preparation method thereof.
In order to solve the technical problem, the invention adopts the following technical scheme:
a colorless transparent polyimide film comprising 2 to 10mol% of a structural unit represented by the following formula (I):
in the formula (I), n is an integer greater than or equal to 1;
the film is doped with glass powder, and the glass powder is solid particles and accounts for 2-8 wt% of the film.
The structural unit shown in the formula (I) is an amino-terminated rigid chain segment, so that the obtained colorless transparent polyimide film has higher heat resistance; in addition, the structural unit shown in the formula (I) contains 2 ester bonds, and the structure has low polarizability, so that the obtained colorless transparent polyimide film has a low dielectric loss factor. In the structural unit represented by the formula (I), n is preferably 5 to 10. The structural unit shown in the formula (I) is polymerized in an aprotic polar solvent through 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl and p-phenyl bis (trimellitate) dianhydride (TAHQ).
The colorless transparent polyimide film of the present invention comprises a polyimide polymer obtained by polymerizing a diamine monomer and a dianhydride monomer, wherein the structural unit represented by the formula (I) is contained in an amount of 2 to 10mol%, and the balance is a polyimide polymer obtained by polymerizing a diamine monomer and a dianhydride monomer,
the diamine monomer is any one or the combination of more than two of 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl (TFMB/TFDB), 2,2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP) and 2,2-bis (4-aminophenyl) hexafluoropropane;
the dianhydride monomer is any one or the combination of more than two selected from 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA), 3,3',4,4' -biphenyl tetracarboxylic dianhydride (s-BPDA), 2,3,3',4' -biphenyl tetracarboxylic dianhydride (a-BPDA), bisphenol A type dianhydride (BPADA) and 1,2,4,5-cyclohexane tetracarboxylic dianhydride (HPMDA).
The preparation method of the colorless transparent polyimide film comprises the following steps:
(1) 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl and terephthalic acid bis (trimellitate) dianhydride are subjected to polycondensation reaction in an aprotic polar solvent to obtain a polymer with a structure shown in the following formula (I);
in the formula (I), n is an integer greater than or equal to 1;
(2) Adding a diamine monomer into the polymer obtained in the step (1), then adding a glass powder dispersion liquid, uniformly mixing, and then adding a dianhydride monomer for reaction to obtain colorless transparent polyamic acid resin; wherein, the first and the second end of the pipe are connected with each other,
the glass powder dispersion liquid is a solution formed by dispersing glass powder in an aprotic polar solvent, and the glass powder is solid particles; the adding amount of the glass powder dispersion liquid is 2-8 wt% of the solid content of the colorless transparent polyamic acid resin by controlling the amount of the glass powder in the obtained colorless transparent polyamic acid resin;
(3) And casting the obtained colorless transparent polyamic acid resin into a film, and then preparing the film according to a conventional process to obtain the colorless transparent polyimide film.
In the step (1) of the preparation method, the structural unit shown in the formula (I) is blocked by an amino group. In the structural unit represented by the formula (I), n is preferably 5 to 10. The molar ratio of 4,4 '-diamino-2,2' -bistrifluoromethylbiphenyl to terephthalic di (trimellitate) dianhydride is typically 1:0.99 to 1.03. The selection and the dosage of the aprotic polar solvent, the temperature and the time of the polycondensation reaction and the like are the same as those of the prior art. Specifically, the aprotic polar solvent may be one or a combination of two or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and γ -butyrolactone. The aprotic polar solvent is used in an amount usually such that the solid content of the colorless and transparent polyamic acid resin obtained in the subsequent step (2) is kept in the range of 10 to 25%, preferably 15 to 20%. The polycondensation reaction is usually carried out at-10 to 50 ℃ and preferably at ordinary temperature, and the reaction time is usually controlled to 4 to 8 hours under the above temperature condition.
In the step (2) of the above production method, the diamine monomer may specifically be any one or a combination of two or more selected from 4,4 '-diamino-2,2' -bis-trifluoromethyl-biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl ] propane and 2,2-bis (4-aminophenyl) hexafluoropropane; the dianhydride monomer may be any one or a combination of two or more selected from 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, bisphenol a dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride. In the step, the adding amount of the diamine monomer and the dianhydride monomer is controlled to control the molar ratio of the total diamine amount to the total dianhydride amount in a reaction system to be 1:0.99 to 1.03, and the dianhydride monomer is preferably added in batches; the temperature and time for the polycondensation reaction after the diamine monomer and the dianhydride monomer are added are the same as those in the prior art, as described above.
In step (2) of the above production method, the particle size of the glass frit is preferably 1800 mesh or smaller, and is more preferably smaller.
In the application, the glass powder is solid spherical particles, the refractive index is 1.46-1.55, and after the glass powder is compounded with a colorless transparent polyimide film (the refractive index is 1.45-1.65), because the refractive indexes of the glass powder and the colorless transparent polyimide film are similar, light rays do not refract when passing through a solid sphere, so that the light transmittance of the obtained colorless transparent polyimide film is ensured not to be reduced; the pencil hardness of the glass powder is 7.0H, and after the glass powder is compounded with the colorless transparent polyimide film (pencil hardness is 1H), the pencil hardness of the surface of the obtained colorless transparent polyimide film is improved, and the thermal expansion coefficient of the obtained film is also reduced.
Dispersing the glass powder in the aprotic polar solvent by adopting the conventional mode and equipment, such as a homogenizer, a grinder, a sand mill, an emulsifying machine or an ultrasonic dispersing machine. The choice of aprotic polar solvent used to prepare the glass frit dispersion is the same as in the prior art, as described above. The aprotic polar solvent is used in an appropriate amount, and the concentration of the glass powder in the glass powder dispersion is preferably controlled to be 8 to 20wt%.
In the step (3) of the preparation method, the obtained colorless transparent polyamic acid resin is defoamed, is subjected to film casting according to a conventional method, and is then stretched or not stretched to perform imidization to obtain the colorless transparent polyimide film. Wherein the imidization operation is the same as the prior art, and the specific imidization parameters can be as follows: keeping the temperature at 120-140 ℃ for 0.5-1 h, then heating to 160-180 ℃ and keeping the temperature for 0.5-1 h, then heating to 250-270 ℃ and keeping the temperature for 0.5-1 h, and then heating to 330-350 ℃ and keeping the temperature for 0.5-1 h; more preferably: 130 ℃/0.5h +170 ℃/0.5h +260 ℃/0.5h +340 ℃/0.5h.
Compared with the prior art, the invention is characterized in that:
1. the structural unit shown in the formula (I) with the end-capped amine group is introduced to endow the obtained colorless transparent polyimide film with lower dielectric loss factor (less than or equal to 0.006 and as low as 0.0045 at 10GHz test frequency).
2. By adding the solid glass powder with the refractive index close to that of the obtained colorless transparent polyimide film, the light transmittance (more than 88%) of the obtained colorless transparent polyimide film is kept, the pencil hardness of the obtained film is improved to more than 3H, and the CTE of the obtained film is reduced to less than 32 ppm/K.
3. The colorless transparent polyimide film can be prepared by adopting the traditional imidization process of the polyimide film, the process is simplified, and the efficiency is higher.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
When a colorless transparent polyimide film is prepared by specifically using the process described in the following examples, the thickness of the film is not limited, and may be various thicknesses such as 12.5. Mu.m, 25. Mu.m, 38. Mu.m, 50 μm, or 75 μm. For comparison of properties, in the following examples and comparative examples, colorless transparent polyimide films having a thickness of 25. + -.3 μm were prepared.
In the following examples and comparative examples, the purity of the related monomers is more than or equal to 99.5 percent; the related glass powder is solid spherical particles with a refractive index of 1.46-1.55.
In Table 2, the tensile strength of the films was tested using a universal tensile machine, specifically according to standard GB/T13542.2-2009.
In Table 2, the light transmittance of the film was measured using a colorless transparent polyimide film having a thickness of about 25 μm, in particular, according to GB T2410-2008 "determination of light transmittance and haze of transparent plastic".
In Table 2, the pencil hardness is measured by the pencil hardness method, in particular with reference to ISO 15184-1998 determination of the hardness of the paint film by the color and varnish pencil method.
In Table 2, the CTE of the film was measured by thermal mechanical analysis in the range of 100 to 200 ℃ according to IPC-TM-650.
In Table 2, the dielectric loss factor (Df) of the thin film is tested according to the standard GB/T13542.2-2009 at 10GHz.
Example 1
(1) Putting 4g of 2000-mesh glass powder and 36g of N, N-dimethylacetamide in a beaker, preparing a dispersion liquid with the concentration of 10wt%, introducing the dispersion liquid into a grinder, grinding for 2h at the speed of 2000 r/min, introducing the dispersion liquid into the beaker, sealing, putting the beaker into an ultrasonic dispersion instrument, performing ultrasonic dispersion for 30min, and testing the glass powder dispersion liquid by a particle size analyzer to obtain glass powder dispersion liquid for later use, wherein the glass powder dispersion liquid does not contain particles larger than 10 microns;
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 2.9g and N, N-dimethylacetamide 364g into a three-neck flask at normal temperature, and stirring for 1h; then 3.68g of p-phenyl bis (trimellitate) dianhydride is added into the three-neck flask and stirred for 1 hour; then, 4,4 '-diamino-2,2' -bistrifluoromethylbiphenyl 48.53g is added into the three-neck flask, and the mixture is stirred for 1 hour; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, adding 44.89g of 3,3',4,4' -biphenyltetracarboxylic dianhydride into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total amount of diamine to the total amount of dianhydride to be 1:0.98, obtaining colorless transparent polyamic acid resin;
(3) The colorless transparent polyimide film is prepared by adopting the traditional imidization process of the polyimide film, namely, the polyamic acid resin is uniformly coated on a bright and clean glass plate by a blade coating method, and imidization is completed in an oven according to a temperature rise program of 130 ℃/0.5h +170 ℃/0.5h +260 ℃/0.5h +340 ℃/0.5h, so as to prepare the CPI film.
Example 2
The same as example 1 except that: replacing the '3,3', 4,4 '-biphenyltetracarboxylic dianhydride' in the step (2) with '2,3,3', 4 '-biphenyltetracarboxylic dianhydride'.
Example 3
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 2.12g and N, N-dimethylacetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then 2.74g of p-phenyl bis (trimellitate) dianhydride is added into the three-neck flask and stirred for 1h; then, adding 4,4 '-diamino-2,2' -bis trifluoromethyl biphenyl 36.11g into the three-neck flask, and stirring for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, then adding bisphenol A type dianhydride 59.032g into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total diamine to the total dianhydride to be 1:1, obtaining colorless transparent polyamic acid resin.
Example 4
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 2.33g and N, N-dimethylacetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then, 2.99g of p-phenyl bis (trimellitate) dianhydride is added into the three-neck flask and stirred for 1 hour; adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 39.53 into the three-neck flask, and stirring for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, adding 4,4' - (hexafluoroisopropylene) diphthalic anhydride 55.15g as a monomer into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total diamine to the total dianhydride to be 1:1, a colorless transparent polyamic acid resin was obtained.
Example 5
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 3.20g and N, N-dimethylacetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then 4.12g of terephthalic di (trimellitate) dianhydride is added into a three-neck flask and stirred for 1 hour; then 4,4 '-diamino-2,2' -bis trifluoromethyl biphenyl 54.39 is added into the three-neck flask and stirred for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, adding other dianhydride monomer 1,2,4,5-cyclohexane tetracarboxylic dianhydride 38.29g into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total diamine to the total dianhydride to be 1:1.01, a colorless transparent polyamic acid resin was obtained.
Example 6
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 1.54g and N, N-dimethylacetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then, 1.47g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour; adding 4,4 '-diamino-2,2' -bis trifluoromethyl biphenyl 49.90 into the three-neck flask, and stirring for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, adding 46.31g of other dianhydride 2,3,3',4' -biphenyl tetracarboxylic dianhydride into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total diamine to the total dianhydride to be 1:1, obtaining colorless transparent polyamic acid resin with the resin viscosity of 3000P.
Example 7
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 5.64g and N, N-dimethylacetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then 7.27g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour; then 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 45.12 is added into the three-neck flask and stirred for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, adding 2,3,3',4' -biphenyl tetracarboxylic dianhydride 41.97g into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total amount of diamine to the total amount of dianhydride to be 1:1, obtaining colorless transparent polyamic acid resin.
Example 8
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 4.54g and N, N-dimethylacetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then, 5.84g of p-phenyl bis (trimellitate) dianhydride is added into the three-neck flask and stirred for 1h; adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 46.49 into the three-neck flask, and stirring for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, then adding 46.49g of 2,3,3',4' -biphenyl tetracarboxylic dianhydride into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total diamine to the total dianhydride to be 1:1, a colorless transparent polyamic acid resin was obtained.
Example 9
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis trifluoromethyl biphenyl 3.78g and N, N-dimethyl acetamide 218.4g into a three-neck flask at normal temperature, and stirring for 1h; then 4.33g of p-phenyl bis (trimellitate) dianhydride is added into the three-neck flask and stirred for 1 hour; then 2,2-bis [4- (4-aminophenoxy) phenyl ] propane 43.63g is added into the three-neck flask and stirred for 1h; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, then adding 4,4' - (hexafluoroisopropylene) diphthalic anhydride 48.26g into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total amount of diamine to the total amount of dianhydride to be 1:1, a colorless transparent polyamic acid resin was obtained.
Example 10
The same as in example 2, except that: the addition amount of the glass powder in the step (1) is 2g.
Example 11
The same as example 2, except that: the addition amount of the glass powder in the step (1) is 8g.
Example 12
The same as example 2, except that: the addition amount of the glass powder in the step (1) was 6g.
Example 13
The same as in example 2, except that: the grain diameter of the glass powder in the step (1) is 3000 meshes.
Example 14
The same as example 2, except that: the grain diameter of the glass powder in the step (1) is 1800 meshes.
Comparative example 1
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) Adding 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl 52.12g and N, N-dimethylacetamide 364g of monomers and stirring for 1h at normal temperature into a three-neck flask; adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, adding 2,3,3',4' -biphenyl tetracarboxylic dianhydride 47.88g into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total amount of diamine to the total amount of dianhydride to be 1:1.01, a colorless transparent polyamic acid resin was obtained.
Comparative example 2
The same as example 1 except that: the step (2) is carried out according to the following operations:
(2) 4,4 '-diamino-2,2' -bis trifluoromethyl biphenyl 3.79g, 2,2-bis [4- (4-aminophenoxy) phenyl ] propane 43.69g and N, N-dimethylacetamide 364g were added to a three-necked flask at room temperature and stirred for 1 hour; then adding the glass powder dispersion liquid prepared in the step (1) into a three-neck flask, stirring and mixing for 1h, then adding 4,4' - (hexafluoroisopropylene) diphthalic anhydride 52.53g into the three-neck flask in 3 batches, stirring for 4h, and controlling the molar ratio of the total diamine to the total dianhydride to be 1:1, obtaining colorless transparent polyamic acid resin.
Comparative example 3
The same as in example 1, except that: step (1) is omitted, and no glass powder is added in step (2), so that the pure colorless transparent polyamic acid resin is obtained.
Comparative example 4
The same as example 2, except that: the grain size of the glass powder in the step (1) is 1700 meshes.
Comparative example 5
The same as example 2, except that: the addition amount of the glass powder in the step (1) is 9g.
Comparative example 6
The same as example 2, except that: the adding amount of the glass powder in the step (1) is 1g.
Comparative example 7
The same as in example 2, except that: in the step (1), '2000-mesh glass powder' is replaced by '2000-mesh ceramic powder'.
The compounding ratio data of the above examples and comparative examples are shown in Table 1 below.
TABLE 1 proportioning table of each example and comparative example
The properties of the colorless and transparent polyimide films obtained in the above examples and comparative examples were measured, and the results are shown in table 2 below.
TABLE 2 film Properties obtained in examples and comparative examples
| Examples | Tensile strength/MPa | Hardness of pencil | Transmittance (a) | CTE/ppm/K | Df，10G |
| Example 1 | 116 | 3H | 88 | 18 | 0.0060 |
| Example 2 | 124 | 3H | 89 | 16 | 0.0055 |
| Example 3 | 102 | 3H | 89 | 32 | 0.0053 |
| Example 4 | 112 | 3H | 90 | 15 | 0.0052 |
| Example 5 | 110 | 3H | 89 | 22 | 0.0055 |
| Example 6 | 135 | 3H | 89 | 19 | 0.0060 |
| Example 7 | 120 | 3H | 88 | 15 | 0.0045 |
| Example 8 | 121 | 3H | 88 | 16 | 0.0058 |
| Example 9 | 106 | 3H | 90 | 28 | 0.0050 |
| Example 10 | 129 | 3H | 89 | 20 | 0.0057 |
| Example 11 | 115 | 4H | 89 | 15 | 0.0056 |
| Example 12 | 116 | 4H | 89 | 16 | 0.0058 |
| Example 13 | 129 | 4H | 89 | 15 | 0.0058 |
| Example 14 | 120 | 3H | 89 | 17 | 0.0059 |
| Comparative example 1 | 126 | 3H | 88 | 22 | 0.0011 |
| Comparative example 2 | 105 | 3H | 87 | 35 | 0.0090 |
| Comparative example 3 | 138 | 1H | 88 | 30 | 0.0070 |
| Comparative example 4 | 118 | 2H | 89 | 18 | 0.0060 |
| Comparative example 5 | 91 | 4H | 85 | 15 | 0.0059 |
| Comparative example 6 | 130 | 2H | 89 | 20 | 0.0058 |
| Comparative example 7 | 120 | 3H | 75 | 18 | 0.0071 |
Comparative examples and comparative examples 1-2 have found that a repeating unit structure polymerized with 4,4 '-diamino-2,2' -bistrifluoromethylbiphenyl and terephthaloyl bis (trimellitate) dianhydride reduces the CPI film dielectric loss factor. Comparative examples and comparative example 3 it was found that the addition of glass frit significantly increased the surface pencil hardness of the CPI film. Comparing the examples with comparative examples 5 to 6, it is found that the addition of excessive glass frit can improve the surface pencil hardness of the CPI film better, but significantly reduce the tensile property of the CPI film and also reduce the light transmittance of the CPI film; adding less glass frit does not result in a CPI film with a better surface pencil hardness.
In summary, the embodiments of the present invention are described in detail, but the invention is not limited thereto. All equivalent changes and simple modifications made in accordance with the claims of the present invention are covered by the claims of the present invention.
Claims (5)
1. A colorless transparent polyimide film comprising a structural unit represented by the following formula (I) in an amount of 2 to 10mol%, and a polyimide polymer obtained by polymerizing a diamine monomer and a dianhydride monomer in the balance:
in the formula (I), n is an integer greater than or equal to 1;
the film is doped with glass powder, and the glass powder is solid particles and accounts for 2 to 8wt% of the film; the granularity of the glass powder is less than or equal to 1800 meshes;
the diamine monomer is any one or the combination of more than two of 4,4 '-diamino-2,2' -bis-trifluoromethyl biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl ] propane and 2,2-bis (4-aminophenyl) hexafluoropropane;
the dianhydride monomer is any one or the combination of more than two of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, bisphenol A dianhydride and 1,2,4,5-cyclohexane tetracarboxylic dianhydride.
2. The colorless transparent polyimide film according to claim 1, wherein n in the formula (I) is from 5 to 10.
3. The method for preparing the colorless transparent polyimide film according to claim 1, comprising the steps of:
(1) 4,4 '-diamino-2,2' -bis (trifluoromethyl) biphenyl and terephthalic acid bis (trimellitate) dianhydride are subjected to polycondensation reaction in an aprotic polar solvent to obtain a polymer with a structure shown in the following formula (I);
in the formula (I), n is an integer greater than or equal to 1;
(2) Adding a diamine monomer into the polymer obtained in the step (1), then adding a glass powder dispersion liquid, uniformly mixing, and then adding a dianhydride monomer for reaction to obtain colorless transparent polyamic acid resin; wherein the content of the first and second substances,
the glass powder dispersion liquid is a solution formed by dispersing glass powder in an aprotic polar solvent, and the glass powder is solid particles; the adding amount of the glass powder dispersion liquid is 2 to 8wt% of the solid content of the colorless transparent polyamic acid resin, wherein the amount of the glass powder in the colorless transparent polyamic acid resin is controlled;
(3) And casting the obtained colorless transparent polyamic acid resin into a film, and then preparing the film according to a conventional process to obtain the colorless transparent polyimide film.
4. The process according to claim 3, wherein in the step (1), n is from 5 to 10.
5. The method according to claim 3, wherein the concentration of the glass frit dispersion in the step (2) is 8 to 20wt%.
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| CN101066839A (en) * | 2007-06-05 | 2007-11-07 | 东华大学 | No-lead glass powder for electrode coating and its prepn process |
| CN105916910A (en) * | 2014-02-14 | 2016-08-31 | 旭化成株式会社 | Polyimide precursor and resin composition containing same |
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